Manufacture of new quaternary ammonium salts



. cNiT EosreTEs PATENT orrice MANUFACTURE OF NEW QUATEBNARY 'AMMONIUM SALTS Henry Alfred Piggott, Blackley, Manchester, England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application January 7, 1938, Se-

' rial No. 183,877. In Great Britain January 14,

1937 5 Claims. (01. 260-289). This invention relates to the manufacture of As alcohols suitable to b sed in their manunew quaternary ammonium oxalates. facture there may P mentioned cetyl 31001101, Some water-soluble quaternary ammonium octdecyl alcohol, e 1k0Syl 21.1601101, ceryl alcohol, Salts col-responding to the formula melissyl alcohol, while as suitable tertiary amines Y 7 there may be mentioned pyridine, the picolines, 5 R--CHz-N the lutidines and quinoline.

where R stands for an aliphatic hydrocarbon q d Organic diluent mentioned above radical, N (tert) stands for the molecule of a y v n ently be provided by using in the tertiary organic amine and X stands for halogen, Synthesis of the initial mat/trial q y of are known compounds for examme, cetyloxytertiary amine in excess of the stoichiometric 10 a: methylpyridinium chloride. Other related water- P and then us ng the reaction mass soluble salts which may be similarly prepared are, directly for conversion into the Oxalate- A erfor example butyloxymethylpyridjmum chloride, natively, other inert organic diluents such as octadecyloxymethylpyridinium chloride and domethanol, ethanol, ethyl t or mixtures decyloxylmethylpyridinium chloride. Also, corof Organic liquids Such as x u s e h ol 15.

responding water-soluble quaternary ammonium and acetone may be used sulphites or pyrosulphites L Where X in the The invention is illustrated but not limited by above formula stands for the sulphite or pyrothe fOllOWing examples in Which t e Parts are sulphite radicle, may be made by reacting in by Weightl- I presence of a tertiary amine, an aliphatic alco- Example 1 20 h01, for example, cetyl alcohol. With Sulphur A pyridine solution of cetyloxymethylpyridindioxide and formaldehyde (see U. S. application q m sulphite is prepared as follows; Serial NO. 140,983). Many Of the above menparts of cetyl alcohol 8 parts of parafornr. tioned salts, although soluble in Water, are difiialdehyde and 64 parts of pyridine are mixed 7 25, cult to purify and to obtain in a crystalline together and heated to C. Sulphur dioxide Condition l is passed into the mixture, the temperature being This invention has as an Oblect to devlse a maintained at 80-90 c. The passing in of sulprocess for the manufacture of new quaternary phur dioxide is continued until a sample f the ammonium oxalates- A further object is to reaction mixture is completely soluble in cold vise a process for the manufacture of-quaternary 30 ammonium salts which w b 9 3 to To the hot pyridine solution of cetyloxymethyland purify. Furt c l appear r pyridinium sulphite obtained as described above a terthere are added 9.3 parts of anhydrous oxalic These Objects are accomplished by the followacid and the mixture is stirred at 85-90 c. until ing invention. I have now found that salts of the oxalic acid has dissolved The sclution is 35 the kind referred to may readily be converted allowed to Stand and 1 until the separation i into water-soluble, crystalline acid oxalates which f crystals is complete The crystalline material are particularly advantageous for use in some is filtered om washed with pyridine and dried texme trfmtment processes' The cetyloxymethylpyridinium acid oxalate thus Accordmg to the present mYentlon I manu' obtained is colourless, crystalline and readily facture new quaternary ammonium acid oxalates soluble in water. by interacting a quaternary ammonium salt of the general formula Example 2 RO-CH2-N(tert)X 4 parts of mixed cetyloxyand octadecyloxy- 45 methylpyridinium chlorides prepared from a where R stands for an aliphatic hydrocarbon radicle of at least sixteen carbon atoms, N(tert) stands for the molecule of pyridine, a C-alkylpyridine or quinoline and X stands for the radicle of an acid other than oxalic acid, with oxalic I acid or a salt thereof in the presence of a liquid oxalic dissolved m 6 parts of warm Pyndme Organic diluent bases. The mixture is thoroughly stirred and The new quaternary lt may th be d, allowed to cool. The white crystalline substance ered as being derivatives of aliphatic alcohols on that p at is filtered oil, washed with methyl the one hand and tertiary am nes on the other. alcohol, then with boiling acetone and dried. 555

technical stearyl alcohol (which is obtained by reducing technical stearic acid) are dissolved by gentle warming in 15 parts of methanol. To this solution there are added 1.1 parts of anhydrous There are thus obtained 3.2 parts of a mixture As many apparently widely different embodij of cetyloxyand octadecyloxy-methylpyridinium ments of this invention may be made without hydrogen oxalates, M. P. 116-118" C. The white departing from the spirit and scope thereof, it crystalline product dissolves in warm water to a is to be understood that I do not limit myself colourless fgagning sglutlon which reacts acid to the specific embodiments thereof, except as towards Congo red and slowly becomes turbid defined in the appended claims. and decomposes on boiling. I claim:

1. Process for the manufacture of new quater- Emmple 3 nary ammonium acid oxalates which comprises 27 parts of octadecyl alcohol, 64 parts of pyn. causing oxalic acid or a salt thereof to react,

dine and 8 parts of paraformaldehyde are stirred in the Presence of an inert liquid Organic dilutogether at 80 C. and sulphur dioxide is passed ent, with a quaternary n u Sa t o t e into the mixture, at such a rate that the temgeneral F perature remains at 84-88" C., until a sample of 0. cH N t -g thet reaction mixture is completely soluble in cold Where R Stands for an aliphatic hydrocarbon Wa radicle of at least sixteen carbon atoms, To the pyndme Solutmn of octadecyloxy' .N(tert) stands for a molecule of the class methylpyndimum Sulphite thus Obtained. there consisting of pyridine, the C-alkylpyridines and are added 10 parts of anhydrous oxalic acid and quinoline and X stands for the radicle of an the mixture is stirred at 85 90 C. until it forms inorganic acid a clear homogeneous liquid. On cooling slowly 2 A compou'nd general follmula F to20 C. during several hours a white crystalline I t; 1 solid separates.-- This is filtered off and recrystanned from methyl .alcohol- Octadecyloxy' wherein R stands for an aliphatic hydrocarbon methylpyridinium acid oxalate is thus obtained radical f at least 16 carbon atoms, N(tert) in h form of silvery Plates of stands for a molecule of the class consisting of which dissolve in warm water to give a clear pyridine, the c 1 1 and qujno1ine,' jfijQRwlL ilQwb reacts Strongly acid to and X stands for the acid-oxalate radical, said Congo red paper. If this solution is boiled, a compound being solublejn warm water t give precipitate is slowly formed. a foaming solution, and being further characat formed in Example 1 s the terized by its ability to precipitate in crystalline Probable formul? form from organic solvents. 7

n 3. A compound of the general formula i R-o-0HTN o-co-coori wherein R stands for an aliphatic hydrocarbon radical of at least 16 carbon atoms, said comie as pound being soluble in warm water to give a The oxalate formed in Example 2 will be a foaming solution, and being characterized by its mixture of the oxalate formed in Example 1 and ability to precipitate in crystalline form from oran oxalate with the probable formula ganic solvents. 45. 4. The compound cetyl-oxy-methyl-pyridinium acid-oxalate, being a crystalline solid, soluble in warm water with an acid reaction to Congo. \N/ 0 5. The compound octadecyloxy-methyl-pyrig, JLL dinium acid-oxalate, being a crystalline solid, soll uble in warm water with an acid reaction to v Congo. "f' i' "I "H11 HENRY ALFRED PIGGOTT.

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